Cf{11 {32 cfcf{11 cf{11 so{11 {11 f and derivatives and polymers thereof

ABSTRACT

The compound CF2 CFCF2CF2SO2F and derivatives thereof are prepared and polymerized to polymers, including copolymers such as with tetrafluoroethylene, which are useful as ion exchange resins.

United States Patent [191 1 Feb. 27, 1973 Grot [ CF2=CFCF2CF2SO2F AND DERIVATIVES AND POLYMERS THEREOF [75] Inventor: Walther Gustav Grot, Chadds Ford,

[73] Assignee: E. J. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: Nov. 26, 1968 [21] Appl. No.: 779,273

Related US. Application Data [63] Continuation-impart of Ser. No. 595,332, Nov. 18,

1966, abandoned.

[52] US. Cl. ....260/79.3 MU, 260/22 R, 260/513 R, 260/543 F, 260/556 F [51] Int. Cl..C07c 143/68, C07c 143/70, C08f 15/02 [58] Field of Search....260/79.3, 543 F, 513 R, 556 F [56] References Cited UNITED STATES PATENTS 3,041,317 6/1962 Gibbs ..260/79.3

Primary Examiner-James A. Seidleck I Assistant Examiner-C. A. Henderson, Jr.

Attorney-Edwin Tocker [57] ABSTRACT The compound CF,=CFCF CF SO F and derivatives thereof are prepared and polymerized to polymers, in cluding copolymers such as with tetrafluoroethylene, which are useful as ion exchange resins.

5 Claims, No Drawings CF; =CFCF CF; S F AND DERIVATIVES AND POLYMERS THEREOF This patent application is a continuation-in-part of U.S. Pat. application Ser. No. 595,332, filed Nov. 18, 1966, now abandoned by the same inventor.

This invention relates to a fluorocarbon compound and more particularly to a fluorocarbon vinyl compound containing sulfonyl fluoride.

This preparation of the compound CF =CFSO F and its copolymerization with fluorinated ethylenes are disclosed in U.S. Pat. No. 3,041,317 to Gibbs et al. The preparation of the compound CF =CF(OCF CF ),,O CF,CF SO F wherein n is l to 3 and its copolymerization with fluorinated ethylenes is disclosed in U.S. Pat. No. 3,282,875 to Connolly et al.

The present invention provides the compound CF =CFCF CF SO M, wherein M is F, Cl, OH, amine or the group OMe wherein Me is alkali metal or quaternary ammonium, and polymers of said compound.

The compound CF =CFCF CF SO F is made by the following procedure:

The compound ,CFQCICFCICF CFCICF COQH (Kel-F acid 683) was decarboxylated via the sodium salt to yield 4,5dichloroperfluoropentene-l according to the procedure of J.S. Fearn et al., J. Polymer Sci. .4- 1,4 131 (1966). This olefin (92 g.) was reacted with an excess (40 to 50 g.) of freshly distilled 80;, for 12 hours. The temperature at the beginning of the reaction was 40C. and at the end, 60C. The reaction product was the sultone (b.p. 60/25 mm.) which was distilled from the reaction medium. The sultone was then added to water and let stand at 25C. for 12 hours to give a 20 percent yield of CF C|CFClCF=CFSO2F. This reaction mixture was heated to 100C. under a stream of 25 weight per cent F in nitrogen to yield CF CICFCICF CF SO F quantitatively. This dichloride was dechlorinated by refluxing (ca. 95C.) with zinc dust in dioxane for 30 minutes to yield 4-fluorosulfonyl perfluorobutene-l, CF =CF CF CF SO F, which was worked-up from the dechlorination reaction mixture by filtration thereof, followed by addition to water to form a lower layer which was washed with water and dried with CaSo,. Further purification is done by vapor phase chromatography or by distillation. The retention time is a 6 foot X A inch col. containing 25 per cent G.E. Silicone SE 30 on Chromosorb at 70C. is 0.7 minute (for air 0.4 minute). The structure of the compound obtained, which is a liquid at room temperature, was confirmed by NMR mass spectral analysis, and infrared analysis (distinguishingbands at 1780 and 1460 cm").

The sulfonyl fluoride com pound of this invention can be converted to the other sulfonyl derivatives disclosed hereinbefore or can be polymerized, followed by conversion of the sulfonyl fluoride side chain group to such other sulfonyl derivatives, if desired, by conventional procedures such as disclosed in U.S. Pat. No. 3,282,875 to Connolly et al.

For example, the sulfonyl fluoride group can be converted to the -SO CI group by slow heating in the presence of phosphorous pentachloride. The sulfonyl fluoride group can be converted to the sulfonate group by hydrolysis with an alkali metal ammonium, or quaternary ammonium hydroxide or carbonate. The alkali metal group can be any alkali metal. Examples of quaternary ammonium groups include the alkyl and alkyl/aryl ammonium groups such as tetramethyl ammonium, tetraethylammonium, phenyltriethylammonium. The sulfonyl fluoride group can be converted to the amide group, SO NH by contacting with ammonia. Preferably, the conversion reactions are carried out on the polymer. When the conversion reactions are carried out on the monomer, preferably the neutralizing compound is in the form of a salt, such as a carbonate.

The compound of this invention is generally but not necessarily polymerized in the sulfonyl fluoride form using a perfluorocarbon solvent and a perfluorinated free radical initiator. Examples of such solvents are the perfluoroalkanes and the perfluorocycloalkanes, such as perfluoroheptane and perfluorodimethylcyclobutane. Examples of such initiators fluoroperoxides and the nitrogen fluorides such as N F The polymerization temperatures will vary from 50 to +200C., depending on the initiator used. Pressure is not critical and is generally employed to control the ratio of any gaseous monomer or comonomer present. Examples of suitable comonomers include the copolymerizable fluorinated ethylenes in which the vinyl group is at least di-substituted with fluorine atoms, such as vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene. Other comonomers can be present in small amounts such as to provide up to about 6 mole per cent thereof in the resultant copolymer, such as the perfluoro(alkyl vinyl ethers) wherein the alkyl group contains from 1 to 6 carbon atoms. Generally, the copolymer will contain at least 0.5 mole per cent of repeat units derived by copolymerization of the sulfonyl-containing monomer of this invention (usually in the -SO F form followed by conversion to SO H), and usually no more than 50 mole per cent of such units are present in the copolymer.

The following polymerization procedure can be employed: approximately equal weight amounts of CF =CFCF CF SO F and CF =CF (total g.) are added to a polymerization vessel containing 200 ml. of perfluorodimethylcyclobutane. About 0.5 g. of difluorodiazine is pressured into the vessel under a N pressure of 800 psi. The mixture is agitated and the temperature slowly raised to 80C. and maintained at that temperature for about an hour. On cooling and evaporation of the solvent, the copolymer is obtained, with the presence of the sulfonyl fluoride monomer units in the copolymer being detectable by infrared analysis.

The sulfonyl-containing compounds of this invention, and polymers, including copolymers containing units derived from such compounds, can be used in the same manner as the vinyl ethers disclosed in U.S. Pat.

include perat al., such as for ion wherein M is F, Cl, OH, amine or the group -OMe wherein Me is alkali metal or quaternary ammonium.

4. The polymer of claim 3 wherein said polymer is a copolymer of a fluorinated ethylene and the monomer of said repeat unit.

5. The polymer of claim 4 wherein said fluorinated ethylene is tetrafluoroethylene. 

2. CF2 CFCF2CF2SO2F .
 3. A polymer containing the repeat unit wherein M is F, Cl, OH, amine or the group -OMe wherein Me is alkali metal or quaternary ammonium.
 4. The polymer of claim 3 wherein said polymer is a copolymer of a fluorinated ethylene and the monomer of said repeat unit.
 5. The polymer of claim 4 wherein said fluorinated ethylene is tetrafluoroethylene. 